1. Field of the Invention
This invention relates to a process of making powders from polyurethaneurea-based spandex and, more specifically, to a process of extruding spandex under specific conditions to produce a powder.
2. Description of Background Art
Recycling and re-using polymeric materials have become important industrial considerations. Such recycled polymers, including polyurethanes and polyurethaneureas, can be used as modifiers for molding resins, hot-melt adhesives, cosmetics, and the like.
Several methods have been used to recycle crosslinked polyurethanes. German Patent 4,309,139 discloses shredding crosslinked polyurethane foams in two steps to form a powder. German Patent 4,309,228 discloses cutting up crosslinked polyurethane foam, pressing the cut foam into 3-mm diameter strands by use of a flat-matrix press, and granulating the strands. German Patent 4,224,164 discloses production and processing of granulated crosslinked polyurethane plastics in an extruder. U.S. Pat. No. 5,669,559 discloses processing precomminuted cross-linked polyurethanes with a roll mill to form powders.
None of the foregoing references, however, discloses the recycling of soft, tacky polyurethaneureas based substantially completely on linear, difunctional ingredients. Their recycling has heretofore been carried out by cryogenic grinding.
It has now been found that a finely divided polyurethaneurea can be prepared by an unexpectedly simple, one-step process from spandex.
The process of the present invention for making a polyurethaneurea powder comprises the steps of:
feeding a polyurethaneurea-based spandex to an extruder having at least one heating zone at a rate less than the maximum feed rate of the extruder; and
extruding the spandex so that it is subjected to an average temperature range and a total residence time range such that the polyurethaneurea is not degraded and the powder is formed.
As used herein, xe2x80x9cspandexxe2x80x9d has its customary meaning, that is, a manufactured fiber in which the fiber-forming substance is a long chain synthetic elastomer comprised of at least 85% by weight of a segmented polyurethane. Due to the extreme difficulty of spinning crosslinked polymers into fiber, the elastomer from which the spandex is prepared is in turn made from bifunctional ingredients such as polymeric glycols, diisocyanates, and one or more difunctional isocyanate-reactive chain extenders.
Polymeric glycols used in making spandex include polyethers such as poly(tetramethyleneether) glycol and poly(tetramethylene-co-3-methyltetra-methyleneether) glycol, polyesters (such as poly(ethylene-co-tetramethylene terephthalate) glycol and poly(2,2-dimethylpropylene dodecanoate) glycol, and polycarbonates such as poly(pentane-1,5-carbonate) glycol and poly(hexane-1,6-carbonate) glycol.
The most commonly used diisocyanate is 1,1xe2x80x2-methylenebis(4-isocyanatobenzene). Useful chain extenders include diols, diamines, and alkanolamines. When diols are used, polyurethanes are formed; when diamines or alkanolamines are used, polyurethaneureas are formed. Unless they are chemically crosslinked, polyurethanes are generally thermoplastic. Even in the absence of chemical crosslinks, polyurethaneureas are generally not thermoplastic in the sense that they cannot be repeatedly melted without considerable degradation. Very small amounts of trifunctional ingredients can sometimes be added during the preparation of the elastomer, for example diethylenetriamine at the parts-per-million level, but this is insufficient to cause significant crosslinking, and the elastomer remains substantially linear. The process of the present invention uses spandex which is based on polyurethaneureas.
It has now been found that a xe2x80x9cfluffyxe2x80x9d, somewhat fibrous powder can be readily prepared in a single step by passing polyurethaneurea-based spandex through an extruder. The polyurethaneurea powder can be finely or relatively coarsely divided depending on the extruder conditions used and can be formed without use of any special die at the outlet of the extruder and without the need for pre- or post-processing. The present process is considerably easier and more economical to carry out than the traditional cryogenic grinding method.
In order to obtain the polyurethaneurea powder without degradation, the temperature experienced by the spandex must be maintained as low as is consistent with forming the desired powder. The range of average temperatures to which the spandex can be subjected during processing is about 170xc2x0-220xc2x0 C., preferably about 180xc2x0-200xc2x0 C., while the total residence time of the spandex in the extruder is about 3.5-22 seconds, preferably about 10-20 seconds. Use of slower extruder speed (rpm) and therefore longer total residence times, about 10-20 seconds, requires lower temperatures within the above ranges in order to form the polyurethaneurea powder without degradation. Even at short total residence times, about 3.5-5 seconds, the average temperature must not exceed about 220xc2x0 C. in order to avoid the formation of discolored clumps. At such total residence times, however, the spandex must be subjected in at least one heating zone of the extruder to a temperature higher than about 210xc2x0 C. in order to modify the morphology of the spandex to form the powder.
Optionally, the first heating zone of the extruder can be used as a pre-heating zone (for example at a machine setting of about 150xc2x0 C.), and the average temperature to which the spandex is subjected can then be measured in subsequent heating zones.
In the process of the present invention, spandex is fed to the extruder at less, than the maximum feed rate the extruder is capable of processing, so that the extruder is slightly xe2x80x9cstarvedxe2x80x9d. If too much material is fed to the extruder, the resulting extrudate is not a powder but rather clumps, and excessive rise in extruder torque is created. The process is not particularly sensitive to such things as a finish on the spandex (for example silicone oil).
The spandex used in the present process can have a decitex of about 11-2500, preferably about 11-155. The size distribution in the finely divided powder is such that at least about 30 wt % has an average length of about 0.1 cm.
The finely divided polyurethaneurea made by the process of the invention can be blended into other polymers. For example, when thermoplastic polymers such as Hytrel(copyright) 5556 polyethererester elastomer (DuPont) or Ultramid(copyright) B-3 polycaprolactam (BASF), both in pelletized form, were blended and extruded with the polyurethaneurea powder of this invention (10-20 weight percent), exhibited increased yield stress, while 10 wt % powder of this invention blended and extruded with Dacron(copyright) 3934 poly(ethylene terephthalate) fiber-grade resin (DuPont) or Elvax(copyright) 40W poly(ethylene-co-vinyl acetate) (DuPont) increased their tensile strengths. Comparable loadings of the powders of this invention increased both the yield stress and the tensile strength of Pellethane(copyright) 90AEF polyurethane molding resin (Ashland Chemical).
In the Examples, unless otherwise noted, a 16-mm Prism extruder (Prism, Staffordshire, UK) having five heatable zones was used. Unless otherwise noted, the machine setting on the first (pre-heating) zone was 180xc2x0 C. The fifth (downstream) zone, usually present as a heated die, was removed and replaced with an unheated 1.5-inch (3.8 cm) tip to protect the operator from sharp edges and moving parts. The remaining three zones were set so that the spandex was subjected to the measured temperatures indicated in the Examples. The throat of the extruder was cooled with room temperature (about 20xc2x0 C.) water, but air was not excluded from the throat. Unless otherwise noted, the xe2x80x9cVacuum Extractionxe2x80x9d screw series was used. The screw had the following sections:
3 deep feed sections
8 regular conveying sections
7 paddles @ 30xc2x0 kneading sections
5 paddles @ 60xc2x0 kneading sections
1 regular conveying section
1 reverse (left hand) section
2 regular conveying sections
10 paddles @ 60xc2x0 kneading sections
3 regular conveying sections and
1 1.5-inch (3.8 cm) diameter tip.
The ratio of the length to the inner diameter of this extruder was 25. The extrudate was caught in pans, and room temperature (approximately 20xc2x0 C.) air was blown over it to cool it. When nitrogen was used to cool the extrudate, the powder became discolored, indicating degradation.
The temperature to which the spandex was subjected was measured (as distinct from the machine setting) at the three middle zones (zones 2, 3, and 4) of the extruder. In the Tables, xe2x80x9cRPMxe2x80x9d refers to the speed at which the extruder was operated, and residence times were calculated from M. Xanthos, xe2x80x9cReactive Extrusion Principles and Practicexe2x80x9d, pp. 222-225, Oxford University Press, 1992. All spandex types used in the Examples were based on polyetherurethaneureas except for Sample 13, which was based on polyester-urethaneurea. xe2x80x9cComp.xe2x80x9d indicates that a sample was a comparison sample and outside the scope of this invention.